Efficiency of Industrially Relevant Atropisomeric Diphosphines in Copper-Catalyzed 1,4-Asymmetric Conjugate Addition of Dialkylzincs to Cyclic or Acyclic Enones or Dienones

Marie S. T. Morin (1) , Thomas Vives (1) , Olivier Baslé (1) , Christophe Crévisy (1) , Virginie Ratovelomanana-Vidal (2) , Marc Mauduit (1)

1 ISCR - Institut des Sciences Chimiques de Rennes
2 IRCP - Institut de Recherche de Chimie Paris

Industrially relevant atropisomeric diphosphines such as 2,2'-bis(diphenylphosphino)-1,1'-binaphthyl (BINAP), 6,6'-bis(diphenylphosphino)-2,2',3,3'-tetrahydro-5,5'-bi-1,4-benzodioxin (SYNPHOS), and 5,5'-bis(diphenylphosphino)-2,2,2',2'-tetrafluoro-4,4'-bi-1,3-benzodioxole (DIFLUORPHOS) have demonstrated their efficiency in the copper-catalyzed asym. conjugate addn. of various dialkylzincs to α-aryl enones, α-aryl dienones, and cyclic dienones. Excellent 1,4- or 1,6-regioselectivities and enantioselectivities (up to 97% ee) were attained, even with challenging sterically hindered Michael acceptors.

Keywords: enones; addition reactions; asymmetric catalysis; copper; dialkylzinc reagents; Phosphines

Domains: Chemical Sciences; Chemical Sciences; Organic chemistry

Marie S. T. Morin, Thomas Vives, Olivier Baslé, Christophe Crévisy, Virginie Ratovelomanana-Vidal, et al.. Efficiency of Industrially Relevant Atropisomeric Diphosphines in Copper-Catalyzed 1,4-Asymmetric Conjugate Addition of Dialkylzincs to Cyclic or Acyclic Enones or Dienones. Synthesis: Journal of Synthetic Organic Chemistry, 2015, 47 (17), pp.2570--2577. ⟨10.1055/s-0034-1378813⟩. ⟨hal-01188236⟩